title: Pressure-monitored headspace analysis combined with compound-specific isotope analysis to measure isotope fractionation in gas-producing reactions.
abstract: BACKGROUND
  Processes that lead to pressure changes in closed experimental systems can dramatically increase the total uncertainty in enrichment factors (ε) based on headspace analysis and compound-specific isotope analysis (CSIA). We report: (1) A new technique to determine ε values for non-isobaric processes, and (2) a general approach to evaluate the experimental error in calculated ε values.
  
  
  METHODS
  ε values were determined by monitoring the change in headspace pressure from the production of CO2 in a decarboxylation reaction using a pressure gauge and measuring the δ(13) C values using CSIA. The statistical error was assessed over shorter reaction progress intervals to evaluate the impact of experimental error on the total uncertainty associated with calculated ε values.
  
  
  RESULTS
  As an alternative to conventional compositional analysis, calculation of CO2 produced during the reaction monitored with a pressure gauge resulted in rate constants and ε values with improved correlation coefficients and confidence intervals for a non-isobaric process in a closed system. Further, statistical evaluation of the ε values as a function of reaction progress showed that uncertainty in data points for reaction progress (f) at late stages of the reaction can have a significant impact on the reported ε value.
  
  
  CONCLUSIONS
  Pressure-monitored headspace analysis reduces the uncertainty associated with monitoring the reaction progress (f) based on estimating substrate removal and headspace dilution during sampling. Statistical calculations over shorter intervals should be used to evaluate the total error for reported ε values.
authors.affiliation: Department of Earth Sciences, University of Toronto, Toronto, Ontario, M5S 3B1, Canada.
authors.forename: Scott O C
authors.initials: SO
authors.lastname: Mundle
authors.forename: Adelle A
authors.initials: AA
authors.lastname: Vandersteen
authors.forename: Georges
authors.initials: G
authors.lastname: Lacrampe-Couloume
authors.forename: Ronald
authors.initials: R
authors.lastname: Kluger
authors.forename: Barbara
authors.initials: B
authors.lastname: Sherwood Lollar